ION EXCHANGE:

EXPERIMENT & DESIGN

Team 18: Caroline Koenig, Herman Tay Hong Cheng, Ryan Tagher, Morgan Walli
CME433: Chemical Engineering Lab II
December 12, 2019
 Agenda
Overview
Background
Batch Experiment
Continuous Experiment
Overall Experimentation
Process Design
Cost Analysis
References
 Ion Exchange Overview

■ Important Application: Remove hazardous materials from wastewater

■ Process of exchanging ions between electrolyte solution and ion exchange material
– Similarly charged ions more attracted to ion exchange material than solution
– Purifies and produces deionized (DI) water by removing unwanted particles from solution
■ Operation Options: Batch or Continuous
■ Regeneration: Running a solution that is more attractive to ions than the exchange material
– Promotes ion exchange from exchange material to new solution

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 Adsorption vs. Absorption
■ A surface phenomenon ■ A bulk phenomenon
■ Exothermic reaction ■ Endothermic reaction
■ Particles attached loosely to the ■ Particles attached tightly or diffused
surface (Weak van der Waals) into the bulk of material
■ Ex: Water purification resin, Air ■ Ex: Cold storage, Refrigerants, Ice
conditioning production

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 Dowex Resin
■ Ion Exchange Material: Resin placed inside column
– Manufactured by Dow Chemical
■ Mesh Sizes Used: 50-100, 100-200 and 200-400
■ "Mesh”: Describes particle size
– Higher # of mesh size = Smaller the particle
– Finer mesh resin = Higher capacity
■ Mobile Ions Used: H+ (Hydrogen Ion)

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 Experimental Objectives
■ Copper Ion (Cu2+ ) purified from copper sulphate (CuSO4) solution
– Used each particle size of Dowex exchange resins
– 3 different resin particle sizes compared
■ Batch Operation: Characterized batch adsorption properties
– Generated calibration curve to relate absorbance with concentration
– Identified most valid isotherm model for batch results
■ Continuous Operation: Characterized continuous ion exchange
– Generated breakthrough curves
– Identified bed heights (used, unused and total), breakthrough and midpoint
times, and lengths of each mass transfer zone

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EXPERIMENTATION:
BATCH OPERATION
 Batch Adsorption: Isotherms

■ Batch Adsorption: Used for treating small quantities

■ Linear Isotherm: q = Kc
𝑞𝑜 𝑐
■ Langmuir Isotherm: 𝑞 = [often used]
𝐾+𝑐
– K, qo: Experimentally determined by (1/c) vs. (1/q) plot
– If Resulting Plot Linear: y-intercept = b = 1/qo and slope = m = K/qo
■ Freundlich Isotherm: q = Kcn
– K, n: Experimentally determined by log(c) vs. log (q) plot
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 Experimental Overview
Batch Operation for 1 Resin Type

0.5 g Resin each

Resin + 10 mL Dilute 0 3 6 9 12 15 18 21 24
g/L
CuSO4 Solution

48 Hours After
Mixture Capped
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 Calibration Curve
■ To measure experimental concentrations: Calibration curve generated
– 3 Dowex resin particle sizes tested: 50-100, 100-200, and 200-400
– Absorbance of each solution measured via Gen5 Microplate Reader
■ From experimental batch data: Concentration vs. Absorbance Reading plot
– Line of best fit equation to find experimental concentrations

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DATA ANALYSIS:
BATCH EXPERIMENT
 Batch Results
50-100 Mesh 100-200 Mesh 200-400 Mesh
0.4 0.3 0.3
kg absorbate/kg absorbent

0.35
0.25 0.25
0.3
0.2 0.2
0.25

0.2 0.15 0.15

0.15
0.1 0.1
0.1
0.05 0.05
0.05

0 0 0
0 10 20 30 0 10 20 30 0 10 20 30

Feed Concentration (g/L)

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 Comparing Isotherm Models

Correlation Values
50-100 mesh 100-200 mesh 200-400 mesh
Linear 0.9627 0.93 0.8608
Freudlich 0.9785 0.9277 0.9266
Langmuir 0.991 0.9514 0.982

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 Isotherm Analysis

Data fits Langmuir isotherm correlation best for all 3 mesh sizes
■ Dow Ex Resin = Cation exchange resin
– Exhibits highest capacity when exchanging alkaline earth or alkali metals
■ Copper Sulfate is not one of these metals
– Models not expected to follow a Langmuir isotherm
■ Results similar to experiment performed by Fresenius Environmental Bulletin
– FEB’s solutions also followed the Langmuir isotherm

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EXPERIMENTATION:
CONTINUOUS OPERATION
 Experimental Overview
Continuous Operation

■ 8.5g/L copper sulphate (CuSO4) continuously fed into column

■ Each column contains different resin mesh size
– 50-100, 100-200 and 200-400
■ Copper ion from feed solution exchanges with hydrogen cation on resin
■ Trial Duration: 45 minutes
■ Experimental Purpose: Extract copper ion (blue) from feed solution
■ Average Feed Flowrates: 4.5mL/30s (C1), 4.6mL/30s (C2), and 4.65mL/30s (C3)

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 Experimental Apparatus
Continuous Operation

Control
Panel
Pump

Dial
50-100 100-200 200-400
Power
Mesh Mesh Mesh
Source

Waste

Feed

Sampling Locations
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 Continuous Operation
Example: Operating Column 1

Control
Panel
Pump

Dial
50-100 100-200 200-400
Power
Mesh Mesh Mesh
Source

Waste

Feed

Sampling Location
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= Resin Before Exchange

= Resin After Exchange

Sampling Method
Continuous Operation

Start Time End Time

0 min 45 min

Sampled after every Sampled after every Sampled after every

5 min 30 s 20 s
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= Resin Before Exchange

= Resin After Exchange

Regeneration
Continuous Operation

1. DI H20 1. CuSO4 1. HCl

Column returns to
condition before
ion exchange
2. DI H20

Before After
Regeneration
Exchange Exchange
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 Continuous Operation Safety
■ Maximum System Feed Pressure: 45 psi
– Pressure continuously monitored to ensure column operated below max
■ Pump Operating Range: 0-200 rpm
■ Emergency Shutdown: On/Off switch on pump
■ Chemical Hazards: Used proper PPE
– HCl = Strong acid, Corrosive to skin, Very dangerous if ingested or inhaled
– Copper sulfate = Corrosive to skin
■ Column Control Dial: Fully locked into a column setting
– Settings = 50-100, 100-200, 200-400, and Waste
– Pressure builds up within apparatus if in-between settings

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 DATA ANALYSIS:
CONTINUOUS EXPERIMENT
 Breakthrough
■ Time when sample concentration reaches 0.01g/L
■ Determined when sample concentration plotted against time
■ Higher breakthrough time results in higher column capacity for adsorption
■ Length between breakthrough and equilibration time depends on mass-transfer rate
■ Steeper slope = Higher mass transfer rate
– Indicates column bed fully utilized

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 Mass Transfer Zone
■ Section of resin where ion exchange actively occurs
■ Steeper breakthrough curve = Faster exchange rate = Smaller mass transfer zone (MTZ)
■ Narrow mass transfer zone = Efficient use of absorbent and cheaper regeneration

Time

Narrow
MTZ

Wide
MTZ

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 Analysis Methods

1. Collected samples
2. Performed trials in triplicate
3. Used calibration curve to determine concentrations
4. Constructed breakthrough curves for each trial
5. Determined breakthrough time (Tb), used bed height (Hb), unused bed height (Hunb)
6. Determined average parameters for each mesh size

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 Analysis Methods
■ Assumed for fixed adsorbent bed:
– Breakthrough curve is symmetrical about C/C 0 = 0.5
– Integral between tb and ts = Area above curve between ts and td
– Time equivalent to total capacity (tt) = Stoichiometric time (ts)
– Time equivalent to usable capacity (tu) = Breakthrough time (tb)

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 Analysis Methods
𝑡𝑢
𝐻𝐵 = 𝐻
𝑡𝑡 𝑇
■ Height of Adsorption Bed (HB)
– (tu/tt) or (tb/ts) = fraction of total bed length used up to break point 𝑡𝑢
𝐻𝑈𝑁𝐵 = 1 − 𝐻𝑇
■ Height of Unused Bed (HUNB) = HUNB-ext 𝑡𝑡
– Unsaturated bed after break point reached
𝐻𝑇 = 𝐻𝑈𝑁𝐵 + 𝐻𝐵
■ Total Bed Height (HT)
𝐻𝑇
■ Bed Fluid Velocity (USH) 𝑈𝑆𝐻 =
𝑡𝑆
■ Length of Mass Transfer Zone (LMTZ) = HUNB-exp
𝐿𝑀𝑇𝑍 = 𝑈𝑆𝐻 𝑡𝑀𝑇𝑍
– Used experimental C/C0 maximums instead of 1
– Total time in the MTZ (tMTZ)

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 Results: 50 to 100 Mesh
■ tb= 1905s
■ ts = 2533s
■ Hb = 97.76mm
■ Hunb-ext = 32.24mm
■ Hunb-exp = 38.75mm

Smallest:
Breakthrough Time
Height of Bed

Largest:
Stoichiometric Time
Height of Unused Bed
Length of MTZ
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 Results: 100 to 200 Mesh
■ tb= 2187s
■ ts = 2421s
■ Hb = 117.4mm
■ Hunb-ext = 12.56mm
■ Hunb-exp = 23.78mm

Intermediate Values:
Between 50-100 & 200-400

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 Results: 200 to 400 Mesh
■ tb= 2300s
■ ts = 2349s
■ Hb = 127.3mm
■ Hunb-ext = 2.677mm
■ Hunb-exp = 14.4mm

Smallest:
Stoichiometric Time
Height of Unused Bed
Length of MTZ

Largest:
Breakthrough Time
Height of Bed
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 OVERALL
EXPERIMENTATION
 Experimental Conclusions
■ Batch Ion Exchange: Copper sulfate solution and Dowex resin follow Langmuir isotherm
■ Continuous Ion Exchange: Higher mesh size = Longer breakthrough time
■ Variation in Results Due To:
– Concentration Inconsistencies
– Regeneration Inconsistencies
■ Improvements for Next Experiment:
– Test different types of resins
– Test at varying temperatures
– Longer trial runs

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PROCESS DESIGN
 Design Problem
■ Current water treatment facility has one ion exchange column
– Capable of processing 150 gallons per day (GPD) of 8.5 g/L copper sulfate solution
■ Facility now must process 1000 GPD
– Goal: Find most economic design to process the increased capacity

For Langmuir isotherms, like this one, the height of the mass-transfer zone is constant and can be
used to scale up when used bed height is large compared to size of mass transfer zone

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 Design Problem
Use number of columns and operating time to determine flowrate

Use bed heights and mass velocity to determine column diameter for each breakthrough time

Calculate regeneration time for HCL and DI water based on bed volumes in existing column

Determine operational and equipment costs

Determine total costs for a 20-year period

Determine number of columns, operating time, and breakthrough time that minimize cost

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 Design Assumptions
Resin and Equipment -
■ Lifespan of resin = 5-10 years (5 assumed in calculations)
■ Piping cost = 45% of Purchased Equipment Cost (PEC)
■ Cost of utilities = 6% of Purchased Equipment Cost (PEC)
■ Integration into existing distributed control system (DCS) = $10,000/column
■ DI water produced in-house = $4,500/column

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 Design Assumptions

Resin and Equipment -

■ 1M HCL produced from 32% HCL using DI water
■ Same mass velocity as experiment
– Column diameters calculated accordingly
■ Feed solution stored by existing equipment until processed
■ Breakthrough time less than 8h for reasonable heights

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 Design Assumptions
Operation -
■ Plant operates 330 days per year
■ 0.25 hours extra per column per cycle
■ 1 operator needed for process, operates 5 processes total using DCS
– Paid $44.30 per hour total ($8.90 for this process)
■ For Regeneration:
– HCL flowrate = 0.02 m3/h
– DI water flowrate = Feed flow rate
– Time needed for regeneration calculated from flowrate and column volume
■ Maintain bed volumes equal to those in the existing column

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 Design Analysis
■ Costs for a 20-year period compared across all possible combinations of breakthrough
time, column number, and operating time using Excel solver and minimum time selected

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 F = 0.16m3/h
Design Solution
■ Existing single column replaced D = 0.172m
■ 8 columns, 1 cycle
■ Dowex 50-100 mesh resin
■ Breakthrough time = 2.96 hours
h = 0.579m Hb = 0.546m
■ Column operated for 10.22 hours/day
– 2.96 hours for feed
– 3.95 hours of regeneration with HCL
– 1.32 hours of rinsing with DI water
– 2 hours extra time

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 Cost Analysis
Columns $ 208,354.20
Resin $ 26,950.14
Piping $ 218,935.04
Pumps $ 135,217.95
DI Water Unit $ 36,000.00
DCS Integration $ 80,000.00
Total Installation Cost $ 705,457.34
Operator Pay $ 32,181.74
Raw Materials $ 899.60
Utilities $ 4,783.58
Total Yearly Operating Cost $ 35,710.12
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 Design Schematic
Each column equipped with:
• Individual solenoid valves connected to DCS
• Pressure and flowrate indicators connected to DCS

Columns operated individually or in any combination allow:

• Continued operation of system if problem/maintenance on column
• Flexibility in amount of feed processed per hour (if requirements/upstream operation change)

Pressure relief valves feed to overflow tank

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43
 Safety for Scale-Up
■ Pressure Relief Valves
– High pressures
■ Pressure and flowrate indicator valves
– Linked to DCS to provide real-time monitoring
■ Solenoid valves
– Controlled both manually and by DCS in case of system malfunction
■ New operating procedures will be written and maintained
– Operators will need to be trained on procedures
– Proper PPE when handling materials and around equipment
– Maintenance schedule

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 Design Alternatives
■ Replace or Keep Existing Column
■ Parallel vs Series
– Series:
■ Shorter columns required
■ Less piping and instrumentation
■ Longer times
– Parallel:
■ Operate with column down
■ More piping and instrumentation
■ Shorter times
■ Other resins could also be tested to
h..further optimize the design
Existing Single Column:
• Costs $1.58/gal at 150 GPD
New Single Column:
•Costs $0.47/gal at 150 GPD
•Pays for itself in 1.5 years
Existing Column with New Optimized Columns:
•Costs $0.23/gal at 1,000 GPD
•$2.6 million over 20 years
Set of 8 New Columns:
•Costs $0.11/gal at 1,000 GPD
•$1.4 million over 20 years
•Savings of $1.2 million over 20 years
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 Design Conclusions

8 New Columns = Cheapest way to meet the new capacity requirements for the facility
– Breakthrough and operating times were optimized
– Meets the new 1,000 GPD processing requirement
– $48/year cheaper than 100-200 mesh, $97/year cheaper than 200-400 mesh
– Replacing existing column saves $1.2 million over 20 years

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Questions?

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 References
• ACROS Organics. (2019, 12 10). Ion Exchange Resin. Retrieved from ACROS Organics:
https://www.acros.com/DesktopModules/Acros_Search_Results/Acros_Search_Results.aspx?search_type=CatalogSearch&SearchString=do w
ex
• Alibaba.com. (2019, 12 10). Industrial grade hydrochloric acid 32%. Retrieved from Alibaba.com: https://www.alibaba.com/product-
detail/Industrial-grade-hydrochloric-acid-32-_62399839453.html?spm=a2700.7724857.normalList.2.90da1ca0DtkTM0&s=p
• Alibaba.com. (2019, 12 10). The production of ultra pure water unit produce type I and type III water.Retrieved from Alibaba.com:
https://www.alibaba.com/product-detail/The-production-of-ultra-pure-
water_62223864239.html?spm=a2700.7724838.2017115.1.78bd648ckcgZh8
• C, R. (2018, March 13). Difference Between Absorption and Adsorption. Retrieved from Bio Differences:
https://biodifferences.com/difference-between-absorption-and-adsorption.html
• Cole-Parmer. (2019, 12 10). Omnifit EZ Chromatography Columns with Two Adjustable Endpieces. Retrieved from Cole-Parmer:
https://www.coleparmer.com/p/omnifit-ez-chromatography-columns-with-two-adjustable-endpieces/67737
• D.Hazenberg, W. (2009, Dec 14). Picking a DCS: Who Decides and How. Retrieved from Control :
https://www.controlglobal.com/articles/2009/pickingdcs0912/
• DOW. (2019, 12 10). DOWEX TM Fine Mesh Spherical Ion Exchange Resins. Retrieved from DOW Water Solutions :
https://www.lenntech.com/Data-sheets/Dowex-50-WX8-50-100-L.pdf
• Keller, M. (2004, March). Water Conditioners: Maximizing Water Softener Efficiencies . Retrieved from Water Conditioning and
Purification: http://archive.wcponline.com/pdf/0304%20Water%20Conditioners.pdf
• Kentucky American Water Company. (2019, June 28). Rates, Charges, Rules and Regulations for Furnishing Water Service. Retrieved
from Kentucky American Water Company:
https://dnnh3qht4.blob.core.windows.net/portals/8/Rates/KAW_water%20rates%20only.pdf?sr=b&si=DNNFileManagerPolicy&sig=YOS4KtoV
1w%2FBujyKj8d5yOm3xgClIbOXAdRB8UksVNA%3D
• Nasef, M. M., & Ujang, Z. (2012). Introduction to ion exchange processes. In Ion exchange technology I (pp. 1-39). Springer, Dordrecht.

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 Experimental Error
Potential Sources of Error

■ Concentration Inconsistences: Errors impact absorbance readings

– Sample sizes (due to pipetting and inaccurate collection)
– Contaminated well plates
– Feed mixture continually refilled 2-3 times per trial
– Concentrated CuSO 4 mixture and feed mixtures remade daily
– Different operators for different columns

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 Experimental Error
Potential Sources of Error

■ Irregular Regeneration: Errors impact breakthrough times

– Different regeneration scenario after each data collection day
– Inconsistent amount of HCl used
– 50-100 mesh and 100-200 mesh resin = From previous years
– 200-400 mesh resin = New this year
– Different timing used per operator (due to qualitative instructions)
– Difficult for equal ion exchange up the bed (middle vs. sides)

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 Additional Design Assumptions

Resin and Equipment -

■ Feed solution density = 8.5 g/L
■ 50-100 mesh = $0.331/g, 100-200 mesh = $0.375/g, 200-400 mesh = $0.408/g
■ Resins have density of 800,922 g/m 3
■ DI water
– DI water unit = $4,500/column installed
– Maximum production capacity = 120 L/hour per column

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 Additional Design Assumptions

Operation -
■ Maximum process operation time = 24 hours/day
■ Total flowrate = 1000 GPD (3.79 m3/day)
– Split between number of columns and hours operated
■ Maximum flow rate per column = 1000 GPD/24 hours = 42 GPH (0.16 m 3/h)
■ Integer number of cycles required
■ Feed run time = Breakthrough time*Number of cycles

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 Particle Sizes

Mesh Particle Size

50 – 100 0.297mm – 0.149mm
100 – 200 0.149mm – 0.074mm
200 – 400 0.074mm –0.037mm

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